Wetting agents for alkaline baths

ABSTRACT

Detergent mixtures comprising a) an alkylsulfonic acid deriving from a light petrol and containing a sulfonic acid group per 7 carbon atoms at most, b) a low-molecular oxalkylation product of a lower alkyl amine and c) a phosphate of alkanols of 4 to 8 carbon atoms are useful as wetting agents for alkaline baths.

United States Patent Landauer et al.

[451 *July 8, 1975 WETTING AGENTS FOR ALKALINE BATHS Inventors: Franz Landauer, Frankfurt am Main;

Claus Beermann, Neu-Isenburg; MartinReuter, Kronberg, Taunus; Karl Heinz Lebkucher, Hoiheim, Taunus; Hubert Kiesling, Schwalbach, Taunus, all of Germany Hoechst Aktiengesellschaft, Frankfurt am Main, Germany Assignee:

Notice: The portion of the term of this patent subsequent to May 1, 1990, has been disclaimed.

Filed: Feb. 12, 1973 Appl. No.: 331,467

Related US. Application Data Continuation-in-part of Ser. No. 99,264, Dec. 17,

1970, Pat. No. 3,730,903, which is a continuation-in-part of Ser. No. 701,119, Jan. 29, 1968, abandoned.

Foreign Application Priority Data Feb. 2, 1967 Germany 1619040 US. Cl. 252/156; 252/117; 252/121; 252/161; 252/554; 8/125; 8/127 [51] Int. Cl Clld 7/12 [58] Field of Search 252/156, 117, 121, 161, 252/554; 23/125, 127

Netherlands 252/5 3 3 Primary ExaminerLeland A. Sebastian Assistant Examiner-B. Hunt Attorney, Agent, or Firm-Curtis, Morris & Safford [5 7] ABSTRACT Detergent mixtures comprising a) an alkylsulfonic acid deriving from a light petrol and containing a sulfonic acid group per 7 carbon atoms at most, b) a lowmolecular oxalkylation product of a lower alkyl amine and c) a phosphate of alkanols of 4 to 8 carbon atoms are useful as wetting agents for alkaline baths.

5 Claims, No Drawings 1,. wETTlNGrAGENTs FOR .ALKALINEBATH'S,

in which R represents an alkyl radical of 2 to 5 carbon atoms, n represents the integer 2 or 3 and m represents a number of l to 2 and c. an ester of phosphoric acid and of alkanols of 4'to 8 carbon atoms, and if desired, further usual auxili-i ary agents. I it is already known form German Auslegeschrift No. 1 ,014,067 that high moljectilaf weight aliphatic sulfonic acids contaiiting tn or tharij'one .sulfonicgacid groupper molecule are used as wttihg agent for 'm'e'rcj'erizingnd h ng. aths.-. Q' f Y Furthermore, islcnown from Grrnafl Pat. No. 955,857 that mixtures of alkyl'sulforiats bf'S to l carbon atoms .in; the alkyhradical and alkyl sulfates, the alkyl radical of whiclizcontaining l0 16- cafbon atoms can be used as wetting agents'= for-mercerizing baths. Additionally, in order-to improve the solubility of the sulfonates in the mercerizing liquors, small amounts of aliphatic alcohols, amines, alkylamines, ether alcohols or naphthene acids can be used as auxiliary solvent.

It has been found that mixtures of a) aliphatic sulfonic acids deriving from light petrol containing on an average one sulfonic acid group per 7 carbon atoms or their alkali metal salts, b) lower alkyl dialkanolamines and c) phosphoric acid esters of alkanols of 4 to 8 carbon atoms for foam reduction, which may be partially saponified, are used as extremely active and clearly soluble wetting agents even in cold alkaline baths.

It was surprising and unforeseeable that the addition of the alkyl dialkanolamines to the mentioned alkyl sul fonic acids or their alkali metal salts leads to such active, clearly soluble wetting agents. The technical advantages of the wetting agent-mixtures to the process of the present invention are, for example, to be seen from the table shown further below. Especially advantageous in industrial use are the highly improved shrinkage values obtained with said mixtures.

Due to the phosphoric acid esters there are obtained mercerizing baths which are practically free of foam. This is especially advantageous when working on yarn mercerizing machines. To the mercerizing or leaching baths prepared by using the mixtures of the present invention other surface active compounds or mercerizing agents can be added, if desired, such as ethylene oxide condensation products or cresols. If it is deemed desirable, other known auxiliaries such as lower alcohols can still be added.

As starting substances for the preparation of the alkyl sulfonic acids, containing per one sulfonic acid group at most 7 carbon atoms, saturated aliphatic hydrocarbons 'areappropriate such,1;f,o example, as light petrol boiling at 30 80?, t. Q

According to the present invention at least one sulfonic acidgroup visintnod-ucecl into .thelight petrol, having anaverage molecular weight of aboutL60. The sulfonic acid alkaligmetal salts are prepared from these hydrocarbons advantageously by sulfo-chlorination according to the Reedprocess and subsequent alkaline saponification; but also the thioureaprocess ofv Sprague andJohnson or the m ethod of Johnson and Douglas as well as-the oxidation of alkyl sulfides with chlorine can be applied (cf. F. Asinger Chemie und Technologie der Paraffinkohlenstoffe, (1956) Berlin, pages 395, 423 4 424). Other methods of introduction of sulfonic acid groups, such as the-'sulfoxidation can be used.

The lowertalkyl dialkanolamine corresponds. to the general formula in which R represents an alkyl radical of 2 5 carbon atoms and'm represents a number of 1 to 2'andf n is 2 or 3. The alkyl dialkanolaminesadvantageously should be soluble in water. There may be used, forexample, n-propyl-diethanolamine, isoamyl-diethanolamine, ethyl-bis- 2-hydroxy-isopropyl -amine n-butyl-bis 2- hydroxypropyl1-amine or preferably buty l or isobutyla mine which "has"b"een reacted 2 52.5 trnoles of ethylene oxide.

Asiphosphoric acid esters which may beaddedthose derived from alito l'io'ls, esp'e'icial-ly' alkanols of 'a rriedium molecular weight, containing about'4='" 8 carbon atoms,

are preferred, for example-trioctylphosphate, in particular tributylph'osphate anditrii'sobutylphosphatc.- These phosphoric acid esters keeptheir activity' evenawhen partially saponified. i a 1 The proportion by weight of the alkyl sulfonates to the alkyl dialkanolamines is to be 1 0.3 to l 5, preferably l 0.8 to 1 2. The amount of the phosphoric acid ester added is l 15 percent, referred to the total of the sulfonates and alkyl dialkanolamines, preferably 2 6 percent.

The wetting agent mixtures according to the process of the present invention are soluble in dilute as well as in highly-concentrated alkaline lyes, as they are used, for example, for mercerizing or leaching of cellulose fibres, and even in the cold.

The following Example serves to illustrate the invention but it is not intended to limit it thereto.

EXAMPLE 230 g of a light petrol sulfochloride which was prepared according to the Reed process by sulfochlorination of a light petrol (boiling at 30- 80C and having an average molecular weight of and which contains 16.9 percent of sulfur and 20.9 percent of chlorine and thus has about 6 carbon atoms per one SO Cl group was added dropwise within one hour at 50- 60C into a solution of 104 g of sodium hydroxide in 1 litre of water. After stirring for 1 hour, the reaction is complete. After filtration of some resinous impurities the solution contains 30 percent of sulfonate.

Preparation of the mercerizing agent solution:

70.5 g of the above-mentioned light petrol sulfonate solution (containing 21.2 g of sulfonate) are mixed, while stirring, with 37.5 g of butyldiethanolamine, 26 g of water and 8 g of triisobutylphosphate. The clear solution then contains 42 percent of surface active agent.

This composition of mercerizing wetting agents is clearly soluble in mercerizing baths of 300 g of sodium hydroxide/litre.

The light petrol sulfonate alone (i.e., without additions) soon creams up in these baths, i.e., it is useless.

1n the following Table the shrinkage values of the product of the present invention of the Example are given. The Table shows that because of good solubility of the products in strong alkaline baths which product combination is obtained according to the present invention, surprisingly good shrinkage values are also obtained.

Table in which R is alkyl of-2 to carbon atoms, nis 2 or 3 and m is a number of l to 2, and

c. about 1 to about percent by weight of a phosphoric acid ester of alkanols of 4 to 8 carbon atoms. 2. A composition as claimed in claim 1, consisting of a. about to about 55 percent by weight of said sulfonic acid or sulfonate,

b. about 40 to about 65 percent by weight of said amine and c. about 2 to about 6 percent by weight of said ester.

Shrinkage values measured in baths of 300 g of sodium hydroxide/litre according to the method given in Praktikum der Textilveredlung, Otto Meechels, page 24, (1949). Springer Verlag, Berlin-Goettingen-Heidelberg shrinkage (in at 15C) after. surface active 30 sec. 60 sec. 120 sec. 18 sec. 240 sec.

agent/litre we clam: 3. A composition as claimed in claiml, wherein the l. Detergent mixture consisting essentially of a. about 10 to about 80 percent by weight of an alkyl sulfonic acid derived from light petrol boiling at 30- 80C or an alkali metal salt thereof, having on an average one sulfonic acid group per 7 carbon atoms at most or a mixturethereof, b. about 20. to about 85 percent by weight of an amine of the formula R N 1 n 2n )m 2 4. A composition as claimed in claim 1, wherein the amine is butyldiethanolamine.

5. A composition as claimed in claim 1, Wh'erein'the ester is triisobu'tylphosphate. 

1. A DETERGENT MIXTURE CONSISTING ESSENTIALLY OF A. ABOUT 10 TO ABOUT 80 PERCENT BY WEIGHT OF AN ALKYL SULFONIC ACID DERIVED FROM LIGHT PETROL BOILING AT 30*- 80*C OR AN ALKALI METAL SALT THEREOF, HAVING ON AN AVERAGE ONE SULFONIC ACID GROUP PER 7 CARBON ATOMS AT MOST OR A MIXTURE THEREOF, B. ABOUT 20 TO ABOUT 85 PERCENT BY WEIGHT OF AN AMINE OF THE FORMULA R-N( (CNH2N-0)M'') 2 IN WHICH R IS ALKYL OF 2 TO 5 CARBON ATOMS, N IS 2 OR 3 AND M IS A NUMBER OF 1 TO 2, AND C. ABOUT 1 TO AAABOUT 15 PERCENT BY WEIGHT OF A PHOSPHORIC ACID ESTER OF ALKANOLS OF 4 TO 8 CARBON ATOMS.
 2. A composition as claimed in claim 1, consisting of a. about 30 to about 55 percent by weight of said sulfonic acid or sulfonate, b. about 40 to about 65 percent by weight of said amine and c. about 2 to about 6 percent by weight of said ester.
 3. A composition as claimed in claim 1, wherein the sulfonic acid is derived from a light petrol having an average molecular weight of about
 70. 4. A composition as claimed in claim 1, wherein the amine is butyldiethanolamine.
 5. A composition as claimed in claim 1, wherein the ester is triisobutylphosphate. 